Preservation process



Patented Apr. 27, 1948;

PRESERVATION IROCESS Kenneth C. D. Hickman, Rochester, N. Y., as-

signor to Distillation Products, Inc, Rochester, N. Y., a corporation of Delaware No Drawing. Original application October 30,

1942, Serial No. 463,896. Divided and this application November 30, 1943, Serial No. 512,367

' 2 Claims. i

This invention relates to improved procedure for the concentration and/or preservation of tocopherol or vitamin E, contained in by-products or portions thereof produced during the vacuuminert gas deodorlzation treatment of vegetable or table or animal oils. Other objects. will appear hereinafter.

These and other objects are accomplished by animal 1 5 my invention which includes hydrogenatingthe In my copending application 321,913, filed complex mixture which contains tocopherol and March 2, 1940, now Patent No. 2,349,269, issued which is derived fromthe inert gas utilized for May 23,1944, of which this application is in part vacuum-inert deodorization. I have found that a continuation, I have described by-products 0bhydrogenation alters the chemical character of tained during the vacuum-inert gas deodorization the interfering substances completely while the treatment of vegetable or animal oils which bytocopherol remains unaltered. Separation of a products contain a relatively large amount of concentrate from the hydrogenated material is tocopherol. During vacuum-inert gas deodorizathen a relatively simple matter. The hydrogenatlon a small amount of matter is volatillzed from tion also yields a product which has substantially the vegetable or animal oil and is carried over more stability than the unhydrogenated material. with the inert gas. This matter can be con- My invention can be applied directly to the densed from the inert gas at any point between crude material obtained from the deoclorization the deodorizer and the exhaust of the vacuum treatment, preferably after removal of water and system. When steam is used as the inert gas the filtering to remove suspended solids. After such material is usually skimmed from the top of the hydrogenation the hydrogenated product may be basin in which the barometric leg drains. It further treated to separate the impurities, i. e., is also usual procedure to condense materials at by distillation, solvent extraction, chromatoan intermediate condenser between the deodographic adsorption, etc. On the other hand, it rizer and the condenser for the steam. This is frequently more desirable to first subject the volatilized material is known as deodorizer crude source material to a, preliminary concensludge, catch-all scum, clabber stock, etctration such as distillation, solvent extraction, It is an exceedingly complex mixture of organic etc., to obtain a partial concentrate. This prodmaterials including free fatty acids, soaps, hydronot then can be hydrogenated and subjected, if carbons, and other numerous materials which I desired, to 'the additional concentrating treathave not as yet identified. ments such as distillation, solvent extraction, As disclosed in my copending application rechromatographic adsorption, and the like. In ferred to above this deodorizer scum can be subeither case the starting material contains sub- .i d to cer in purification treatments i rstances which interfere with the subsequent sepder to concentrate the tocopherol c n ained aration or stability and hydrogenation converts therein. However, I have found that there are thes substances into materials having a. substances present in the refinery scum which so pletely different chemical character so that they nearly resemble the tocopherols in chemical and no longer exert their undesirable properties. physical properties that distillation and solvent The hydrogenation treatment is preferably 2. treatments Will not effect separation 0f 40 catalytic reduction in the presence of a hydropher l therefrom. This has preven ed ec genation catalyst such as nickel, silver, platinum, nomical p paration of concentrates, particularly etc., under super atmospheric pressure. A presof high concentration. sure of about 25 to 2000 lbs. is usually employed This invention has for its object to overcome although Smaller or greater pressure can b the above difficulties-Another object is to provide used Temperatures of between about t improved procedure for concentrating tocopherol 250 are preferr d especially temperatures b contained in refinery scum and/0r concentrates tween about 150 and 200 C., but lower or higher derived therefrom. A still further object is to temperatures may be used. It is best that the provide improved procedure for concentrating hydrogenation treatment he continued until suband/or preserving complex mixtures which constantlally complete hydrogenation is obtained.

. 3 v It is to be understood. however, that partial hydrogenation efiects a marked improvement as to separation and stability and is to be included within the scope of my invention. Chemical reduction with nascent hydrogen may be employed, if desired, but is not as satisfactory or economical a process as catalytic hydrogenation.

EXAMPLE 1 Refinery scum containing about 3.6% tocopherol was dried under vacuum in a steam jacketed container. The product was preliminarily distilled under high vacuum to strip ofi? 20-30% of volatile impurities. The residue containing about 4.5% tocopherol was distilled in a high vacuum unobstructed path still to separate a tocopherol fraction which was winteredto remove stearine. This material contained approximately 41.7% tocopherol and was hydrogenated at 160 C. in the presence of 1.0% by weight of Rufert nickel catalyst containing .2% active nickel for 1 /2 This was dissolved in five volumes of acetone and cooled to -50 C. The granular precipitated solids were filtered and the filtrate was evaporated. The residue contained 78.7% mixed tocopherols (95.7 recovery). Thus, the potency of the tocopherol concentrate was doubled by the purification procedure. tion of the same but unhydrogenated distillate in acetone gave a difiicultly filterable mass. The filtrate on evaporation gave a residue whose tocopherol potency was only higher than that of the concentrate before cooling in acetone. Thus, hydrogenation markedly increased the concentration effected by solvent extraction. Instead of acetone other vitamin E solvents such as low molecular weight alcohols, petroleum ether, etc., may be used.

EXAMPLE 2 ditions and the percentage of tocopherols remaining after various periods of time was determined by the Emmerie-Engel assay procedure.

hours at 50 lbs. hydrogen pressure.

A similarly cooled solu- Relative rate of decomposition of hydrogenated and unhydrogenated fraction in swift stability test The improved tocopherol products described herein can be used to stabilize oxidizable. substances especially animal and vegetable fats or oils such as shortenings, including lard Because of the increased stability as a result of the reduction a greater resistance to oxidation is imparted to the oxidizable substance to which the tocopherol-containing product is added. Hydrogenated tocopherol products from crude or refined scum may be utilized in this way, Likewise the crude or refined, but unhydrogenated scum may be added to the oxidizable material such as shortening and the entire mixture hydrogenated to obtain a mixture of improved stability.

This application is a division of my application 463,896, filed October, 30, 1942, now Patent No. 2,349,789, issued May 23, 1944.

What I claim is:

1. The process of stabilizing an oxidizable substance which comprises incorporating in the oxidizable substance an antioxidant comprising hydrogenated deodorizer scum, which scum is lighter-than-water, contains tocopherol and is obtained from the steam after it has been passed through a fat which contains tocopherol, during vacuum-steam deodorization of said fat.

2. The process of stabilizing a shortening which comprises in combination hydrogenating a lighter-than-water complex mixture which contains tocopherol and which is derived from the steam after it has been passed through a member of the group consisting of tocopherol-containing vegetable and animal oils during vacuumsteam deodorization and adding a small amount of the hydrogenated mixture to the shortening to be stabilized.

KENNETH c. D. HICKMAN.

REFERENCES crrEn UNITED STATES PATENTS Name Date Jakobsen Nov. 28, 1944 Number 

